Organosilicone derivatives of amino hydroxybenzophenones and their use as uv-a filters in cosmetic preparations

ABSTRACT

The present invention relates to organosilicone derivatives of amino hydroxybenzophenones, a process for their preparation thereof, a cosmetic compositions comprising the organosilicone derivative and the use thereof for protecting hair and/or skin from damage caused by UV-A irradiation.

The present invention relates to organosilicone derivatives of aminohydroxybenzophenones, to a process for their preparation, compositionscomprising these derivatives and the use thereof.

More particularly, the invention relates to organosilicone compoundscomprising a unit of formula I

wherein

a is 0, 1 or 2,

R¹ is hydrogen, a saturated or unsaturated C₁-C₃₀hydrocarbon group or atrimethylsilyloxy group; and

-   -   Z is an amino substituted hydroxybenzophenone of formula III        wherein

R³ and R⁴ independently are hydrogen, C₁-C₂₀alkyl, C₂-C₂₀alkenyl,C₃-C₁₀cycloalkyl or C₃-C₁₀cycloalkenyl or R³ and R⁴, together with thenitrogen atom they are bound to, form a 5 to 6 membered ring;

X is —O— or —NR⁵— wherein R⁵ is hydrogen, C₁-C₂₀alkyl, C₂-C₂₀alkenyl,C₃-C₁₀cycloalkyl or C₃-C₁₀cycloalkenyl; and

Y is a divalent C₃-C₁₂alkylene or alkenylene chain;

and, optionally, a unit of formula II

wherein

b is 0, 1, 2, 3; and

R² is hydrogen, a saturated or unsaturated C₁-C₃₀hydrocarbon group or atrimethylsilyloxy group.

Suitable organosilicone compounds are polymeric materials which maybehomopolymers consisting only of such units of formula I, or they may becopolymers containing both units having either the general formula I orII. The units of formula I may be distributed randomly in anorganosiloxane polymer, they may be the end blocking units of thepolymer or they may be located at the end of the polymer and pending ina chain of the polymer at the same time. The organosilicone compoundsmay vary from freely flowing liquids to highly viscous gum-likematerials or resinous solids.

If a is 2 the two substitutents R¹ may be identical or different. If bis 2 or 3 the two or three substituents R² may be identical ordifferent. If the polymer contains more than one unit of formula I thesubstituents R¹ may be identical or different from unit to unit. If thepolymer contains more than one unit of formula II the substituents R²maybe identical or different from unit to unit.

Examples for a saturated or unsaturated C₁-C₃₀hydrocarbon group includeC₁-C₃₀alkyl such as methyl, ethyl, propyl and butyl; C₂-C₃₀alkenyl suchas vinyl and allyl; and unsubstituted or substituted aryl such asphenyl, alkaryl and alkoxyphenyl. The hydrocarbon group is unsubstitutedor substituted by, e.g. halogen, e.g. a halogenated C₁-C₁₈hydrocarbongroup.

Alkyl and alkenyl may be straight chain or branched, e.g. methyl, ethyl,3-propyl, 2-propyl, 2-methyl-3-propyl, 3-butyl, 4-butyl, 4-pentyl,5-pentyl, 6-hexyl, 2-propen-2-yl, 2-propen-3-yl, 3-buten-3-yl,3-buten-4-yl, 4-penten-4-yl, 4-penten-5-yl, (3-methyl)-penta-2,4-dien-4or 5-yl, 11-dodecen-11-yl.

Examples for cycloalkyl and cycloalkenyl include cyclopropyl,2-methyl-cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cyclopropenyl, cyclobutenyl, cyclopentenyl,(3-methyl)-cyclopenta-2,4-dienyl and 11-cyclododecenyl.

The terms “divalent C₃-C₁₂alkylene chain” and “divalent C₃-C₁₂alkenylenechain” mean linker groups, in particular linker groups which link the UVabsorbing chromophoric residue to the silane, oligosiloxane orpolysiloxane moiety. Examples for C₃-C₁₂alkylene include straight chainor branched saturated hydrocarbon residues such as 3-propylene,2-propylene, 2-methyl-3-propylene, 3-butylene, 4-butylene, 4-pentylene,5-pentylene, 6-hexylene, and the like. Examples for C₃-C₁₂alkenyleneinclude unsaturated hydrocarbon residues containing at least one doublebond, such as for example, 2-propen-2-ylene, 2-propen-3-ylene,3-buten-3-ylene, 3-buten-4-ylene, 4-penten-4-ylene, 4-penten-5-ylene,(3-methyl)-penta-2,4-dien-4 or 5-ylene, 11-dodecen-11-ylene, and thelike. The divalent alkylene or alkenylene chains may be interrupted byone or several oxygen atoms. Examples of oxygen interrupted linkergroups are e.g. 2-ethyloxy-eth-2-ylene, 4-butyloxy-eth-2-ylene or3,6-dioxa-8-octylen. Particularly preferred linkers are—CH═CH—(CH₂)_(n)—, —C(CH₂)—(CH₂)_(n)—, —CH₂—CH₂—(CH₂)_(n)— and—CH(CH₃)—(CH₂)_(n)— wherein n is an integer from 0 to 10.

In the organosilicone compounds of the invention the followingpreferences apply independently, collectively or in any combination orsub-combination:

(a) organosilicone compounds wherein the number of units of formula I islimited to a maximum of 50%, more preferably of 10 to 40%, mostpreferably 30 to 40% of the total number of siloxane units in themolecule;

(b) liquid substantially linear organosiloxane homopolymers andcopolymers, for example those having a viscosity from 50-20000 m²/s;

(c) organosilicone compounds wherein in the units of formula I thefollowing significances apply independently, collectively or in anycombination or sub-combination:

(c1) a is 1;

(c2) R¹ is methyl in 80%, preferably 100% of units of formula I;

(c3) Y is 2-propylene, 3-propylene, 2-propen-2-ylene, 2-propen-3-ylene,4-butylene or 3-buten-4-ylene, preferably 2-propen-2-ylene or2-propen-3-ylene;

(c4) X is —O—;

(c5) R³ and R⁴ are ethyl;

(d) organosilicone compounds wherein in the units of formula II thefollowing significances apply independently, collectively or in anycombination or sub-combination:

(d1) preferably at least two units of formula II are present;

(d2) b is 2;

(d3) R² is methyl in 80%, preferably 100% of units of formula II.

When a=1 and b=2 the organosilicone compound is a substantially linearor cyclic diorgano-siloxane polymer. However, if the diorganosiloxane isa substantially linear polymer at least two endblocking units must bepresent, thus requiring either the presence of two units in which a hasa value of 2 or two units in which b is 3.

A preferred linear diorgano-siloxane polymer (hereinafter: COMPOUND) isa polymer comprising one structural unit of formula IVa and onestructural unit of formula IVb

s units of formula IVc

and r units of formula IVd

wherein

Z is as defined above;

R¹, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ independently are as defined above forR²;

B and B′ independently are a group Z or a group R²;

r is an integer from 0 to 200; and

s is an integer from 0 to 50, wherein at least B or B′ is Z when s is 0.

The compounds of the invention may be prepared by hydrosilylation of anorganosilicone compound in which each unit of formula I is replaced by aunit having the formula VI (hereinafter: SiH derivatives).

SiH derivatives are well known in the silicone industry and arecommercially available. They are described, for example, in thefollowing patents: U.S. Pat. No. 3,220,972, U.S. Pat. No. 3,697,474 andU.S. Pat. No. 4,340,709.

The hydrosilylation may be carried out by reacting the SiH derivative inthe presence of a transition metal catalyst, e.g. platinum on charcoalor a platinum complex catalyst, such as e.g. divinyl-tetramethyldisiloxane platinum complex with a compound of formula VII

in which R³, R⁴ and X are as defined for formula III and Y′ has the samedefinition as Y in formula III, but is terminated either with a doubleor a triple bond. The addition may proceed at both positions of theunsaturated carbon-carbon bond, leading to isomeric mixtures oforganosilicone products e.g. containing exo and endo double bonds.

The hydrosilylation may be performed in a suitable reaction solvent,e.g. in isopropanol or toluene. The reactants may be present in aboutequal molar amounts. The reaction may be run at an elevated temperature,e.g. in a range of from 40° C. to 150° C., preferably from 60° C. to100° C., e.g., at about 80° C.

Compounds of formula VII are generally known and may be prepared, e.g.,according to the procedure described in EP 1,046,391 by acylation of thecorresponding amino substituted phenols followed by reaction with therespective alcohol or amine such as propinol, allyl alcohol, vinylalcohol, prop-2-ynyl amine or vinyl amine. Exemplary aminohydroxybenzophenones which are particulary suited for the preparation ofthe compounds of the invention include2-(4-diethylamino-2-hydroxybenzoyl)benzoic acid prop-2-ynyl ester,2-(4-diethylamino-2-hydroxybenzoyl)benzoic acid ally ester,2-(4-diethylamino-2-hydroxybenzoyl)benzoic acid vinyl ester and2-(4-diethylamino-2-hydroxybenzoyl)benzoic acid N-prop-2-ynyl benzamide.

The compounds of the present invention have adsorption maxima in theUV-A region and are effective in absorbing ultra violet radiation in theUV-A range (320-400 nm) which makes them particularly suitable for usein cosmetic sunscreen preparations where absorption in the UV-A range isparticularly desirable.

Thus, the present invention also relates to compositions comprising thenovel organosilicone compounds, formulated into a suitable support orsubstrate. Typically, the compositions of the invention are adopted forprotecting a material that is sensitive to ultraviolet radiation, inparticular solar radiation, such as skin and/or hair and comprises aneffective photoprotective amount of an organosilicone compound of theinvention.

For the preparation of light screening agents, especially ofpreparations for dermatological and/or cosmetic use, such as skinprotection and sunscreen formulations for everyday cosmetics a compoundof this invention may be incorporated in auxiliary agents, e.g. acosmetic base, which are conventionally used for such formulations.Where convenient, other conventional UV-A and/or UV-B screening agentsmay also be added. The combination of UV filters may show a synergisticeffect. The preparation of said light screening agents is well known tothe skilled artisan in this field. The concentration of UV filters isnot critical. For example, the amount of compounds of the presentinvention and optionally an additional hydrophilic and/or lipophilicUV-A or UV-B screening agent other than the compounds described in thisinvention maybe in the range of from 0.5 to 12% by weight of the totalcomposition. These additional screening agents are advantageouslyselected from the compounds listed below without being limited thereto:

Examples of UV B screening agents, i.e. substances having absorptionmaxima between about 290 and 320 nm, which come into consideration forcombination with the compounds of the present invention are for examplethe following organic and inorganic compounds: acrylates such as2-ethylhexyl 2-cyano-3,3-diphenylacrylate (octocrylene, PARSOL® 340),ethyl 2-cyano-3,3-diphenylacrylate and the like; camphor derivativessuch as 4-methyl benzylidene camphor (PARSOL® 5000), 3-benzylidenecamphor, camphor benzalkonium methosulfate, polyacrylamidomethylbenzylidene camphor, sulfobenzylidene camphor, sulfomethyl benzylidenecamphor, therephthalidene dicamphor sulfonic acid and the like;cinnamate derivatives such as octyl methoxycinnamate (PARSOL® MCX),ethoxyethyl methoxycinnamate, diethanolamine methoxycinnamate (PARSOL®Hydro), isoamyl methoxycinnamate and the like as well as cinnamic acidderivatives bond to siloxanes; p-aminobenzoic acid derivatives, such asp-aminobenzoic acid, 2-ethylhexyl p-dimethylaminobenzoate,N-oxypropylenated ethyl p-aminobenzoate, glyceryl p-aminobenzoate;benzophenones such as benzophenone-3,benzophenone-4,2,2′,4,4′-tetra-hydroxy-benzophenone,2,2′-dihydroxy-4,4′-dimethoxybenzophenone and the like; esters ofbenzalmalonic acid such as di(2-ethylhexyl)4-methoxybenzalmalonate;esters of 2-(4-ethoxy anilinomethylene)propanedioic acid such as2-(4-ethoxy anilinomethylene)propanedioic acid diethyl ester asdescribed in EP 895,776; organosiloxane compounds containingbenzmalonate groups as described in EP 358,584, EP 538,431 and EP709,080; drometrizole trisiloxane (MEXORYL XL); pigments such asmicroparticulated TiO₂, and the like, wherein the term“microparticulated” refers to a particle size from about 5 nm to about200 nm, particularly from about 15 nm to about 100 nm, and which TiO₂particles may be coated by metal oxides such as e.g. aluminum orzirconium oxides or by organic coatings such as e.g. polyols, methicone,aluminum stearate, alkyl silane; imidazole derivatives such as e.g.2-phenyl benzimidazole sulfonic acid and its salts (PARSOL®HS). Salts of2-phenyl benzimidazole sulfonic acid are e.g. alkali salts such assodium- or potassium salts, ammonium salts, morpholine salts, salts ofprimary, sec. and tert.amines like monoethanolamine salts,diethanolamine salts and the like; salicylate derivatives such asisopropylbenzyl salicylate, benzyl salicylate, butyl salicylate, octylsalicylate (NEO HELIOPAN OS), isooctyl salicylate or homomenthylsalicylate (homosalate, HELIOPAN) and the like; triazine derivativessuch as octyl triazone (UVINULT-150), dioctyl butamido triazone (UVASORBHEB), bis ethoxyphenol methoxcyphenyl triazine (TINOSORB S) and thelike; a polysiloxane containing a UV-B chromophor like e.g. Polysilicone15 (Dimethicodiethylbenzalmalonate or Parsol SLX).

Examples of UV A screening agents i.e. substances having absorptionmaxima between about 320 and 400 nm, which come into consideration forcombination with the compounds of the present invention are for examplethe following organic and inorganic compounds: dibenzoylmethanederivatives such as 4-tert.butyl-4′-methoxydibenzoylmethane (PARSOL®1789), dimethoxydibenzoylmethane, isopropyldibenzoylmethane and thelike; benzotriazole derivatives such as2,2′-methylene-bis-(6-(2H-benzotriazole-2-yl)-4-(1,1,3,3,-tetramethylbutyl)-phenol(TINOSORB M) and the like; phenylene-1,4-bis-benzimidazolsulfonic acidsor salts such as 2,2-(1,4-phenylene)bis-(1H-benzimidazol-4,6-disulfonicacid) (NEOHELIOPAN AP); amino substituted hydroxybenzophenones such as2-(4-diethylamino-2-hydroxy-benzoyl)-benzoic acid hexylester asdescribed in EP 1,046,391; pigments such as microparticulated ZnO andthe like, wherein the term “microparticulated” refers to a particle sizefrom about 5 nm to about 200 nm, particularly from about 15 nm to about100 nm, and which ZnO particles may be coated by metal oxides such ase.g. aluminum or zirconium oxides or by organic coatings such as e.g.polyols, methicone, aluminum stearate, alkyl silane.

As dibenzoylmethane derivatives have limited photostability it may bedesirable to photostabilize these UV-A screening agents. Thus, the term“conventional UV-A screening agent” also refers to dibenzoylmethanederivatives such as e.g. PARSOL® 1789 stabilized by, e.g.,3,3-diphenylacrylate derivatives as described in EP 514,491 and EP780,119; benzylidene camphor derivatives as described in U.S. Pat. No.5,605,680; organosiloxanes containing benzmalonate groups as describedin EP 358,584, EP 538,431 and EP 709,080.

The compositions of the invention may also contain usual cosmeticadjuvants and additives, such as preservatives/antioxidants, fattysubstances/oils, water, organic solvents, silicones, thickeners,softeners, emulsifiers, additional sunscreens, antifoaming agents,moisturizers, fragrances, surfactants, fillers, sequestering agents,anionic, cationic, nonionic or amphoteric polymers or mixtures thereof,propellants, acidifying or basifying agents, dyes, colorants, pigmentsor nanopigments, in particular those suited for providing an additionalphotoprotective effect by physically blocking out ultraviolet radiation,or any other ingredients usually formulated into cosmetics, inparticular for the production of sunscreen/antisun compositions. Thenecessary amounts of the cosmetic and dermatological adjuvants andadditives may, based on the desired product, easily be chosen by askilled artisan in this field and will be illustrated in the examples,without being limited hereto.

An additional amount of antioxidants/preservatives is generallypreferred. All known antioxidants usually formulated into cosmetics maybe used. Especially preferred are antioxidants chosen from the groupconsisting of amino acids (e.g. glycine, histidine, tyrosine,tryptophane) and their derivatives, imidazole (e.g urocanic acid) andderivatives, peptides such as D,L-carnosine, D-carnosine, L-carnosineand derivatives (e.g. anserine), carotinoids, carotenes (e.g.α-carotene, β-carotene, lycopene) and derivatives, chlorogenic acid andderivatives, liponic acid and derivatives (e.g. dihydroliponic acid),aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxine,glutathione, cysteine, cystine, cystamine and its glycosyl-, N-acetyl-,methyl-, ethyl-, propyl-, amyl-, butyl- and lauryl-, palmitoyl-; oleyl-,y-linoleyl-, cholesteryl- and glycerylester) and the salts thereof,dilaurylthiodipropionate, distearylthiodipropionate, thiodipropionicacid and its derivatives (ester, ether, peptides, lipids, nucleotides,nucleosides and salts) as well as sulfoximine compounds (such asbuthionine sulfoximine, homocysteine sulfoximine, buthionine sulfone,penta-, hexa-, heptathionine sulfoximine) in very low compatible doses(e.g. pmol/kg to μmol/kg), additionally (metal)-chelators (such asγ-hydroxyfatty acids, palmic-, phytinic acid, lactoferrin),α-hydroxyacids (such as citric acid, lactic acid, malic acid), huminicacid, gallic acid, gallic extracts, bilirubin, biliverdin, EDTA, EGTAand its derivatives, unsaturated fatty acids and their derivatives (suchas γ-linoleic acid, linolic acid, oleic acid), folic acid and itsderivatives, ubiquinone and ubiquinol and their derivatives, vitamine Cand derivatives (such as ascorbyl palmitate and ascorbyltetraisopalmitate, Mg-ascorbyl phosphate, Na-ascorbyl phosphate,ascorbyl acetate), tocopherol and derivates (such as vitamin-E-acetate,nat. vitamin E and mixtures thereof), vitamin A and derivatives (vitaminA palmitate and acetate) as well as coniferylbenzoat, rutinic acid andderivatives, α-glycosylrutin, ferulic acid, furfurylidene glucitol,butyl hydroxytoluene, butyl hydroxyanisole, trihydroxybutyrophenone,urea and its derivatives, mannose and derivatives, zinc and derivatives(e.g. ZnO, ZnSO₄), selenium and derivatives, (e.g. selenomethionine)stilbenes and derivatives (such as stilbenoxide, transstilbenoxide) andsuitable derivatives (salts, esters, ethers, sugars, nucleotides,nucleosides, peptides and lipids) of the named active ingredients. Oneor more preservatives/antioxidants may be present in an amount of about0.01 wt. % to about 10 wt. % of the total weight of the composition ofthe present invention. Preferably, one or morepreservatives/antioxidants are present in an amount of about 0.1 wt. %to about 1 wt. %.

Examples of emulsifiers that may be used in the present invention inorder to form O/W, W/O, O/W/O or W/O/W emulsions/microemulsions includesorbitan oleate, sorbitan sesquioleate, sorbitan isostearate, sorbitantrioleate, polyglyceryl-3-diisostearate, polyglycerol esters ofoleic/isostearic acid, polyglyceryl-6 hexaricinolate,polyglyceryl-4-oleate, polygylceryl-4 oleate/PEG-8 propylene glycolcocoate, oleamide DEA, TEA myristate, TEA stearate, magnesium stearate,sodium stearate, potassium laurate, potassium ricinoleate, sodiumcocoate, sodium tallowate, potassium castorate, sodium oleate, andmixtures thereof. Further suitable emulsifiers are phosphate esters andthe salts thereof such as cetyl phosphate (Amphisol® A), diethanolaminecetyl phosphate (Amphisol®), potassium cetyl phosphate (Amphisol® K),sodium glyceryl oleate phosphate, hydrogenated vegetable glyceridesphosphate and mixtures thereof. Furthermore, one or more syntheticpolymers may be used as an emulsifier. For example, PVP eicosenecopolymer, acrylates/C₁₀₋₃₀-alkyl acrylate crosspolymer,acrylates/steareth-20 methacrylate copolymer, PEG-22/dodecyl glycolcopolymer, PEG-45/dodecyl glycol copolymer, and mixtures thereof. Thepreferred emulsifiers are cetyl phosphate (Amphisol® A), diethanolaminecetyl phosphate (Amphisol®), potassium cetyl phosphate (Amphisol® K),PVP eicosene copolymer, acrylates/C₁₀₋₃₀alkyl acrylate crosspolymer,PEG-20 sorbitan isostearate, sorbitan isostearate, and mixtures thereof.Emulsifiers are present in a total amount of about 0.01 wt. % to about20 wt. % of the total weight of the composition of the presentinvention. Preferably, about 0.1 wt. % to about 10 wt. % of emulsifierare used.

The lipid phase may advantageously be chosen from: mineral oils andmineral waxes; oils such as triglycerides of caprinic acid or caprylicacid, preferably castor oil; oils or waxes and other natural orsynthetic oils, in a preferred embodiment esters of fatty acids withalcohols e.g. isopropanol, propyleneglycol, glycerin or esters of fattyalcohols with lower carboxylic acids or fatty acids; alkylbenzoates;silicone oils such as dimethylpolysiloxane, diethylpolysiloxane,diphenylpolysiloxane, cyclomethicone and mixtures thereof.

Exemplary fatty substances which may be incorporated into the oil phaseof the emulsion, microemulsion, oleo gel, hydrodispersion orlipodispersion of the present invention are advantageously chosen fromesters of saturated and/or unsaturated, linear or branched alkylcarboxylic acids with 3 to 30 carbon atoms, and saturated and/orunsaturated, linear and/or branched alcohols with 3 to 30 carbon atomsas well as esters of aromatic carboxylic acids and of saturated and/orunsaturated, linear or branched alcohols of 3-30 carbon atoms. Suchesters may advantageously be selected from octylpalmitate, octylcocoate,octylisostearate, octyldodeceylmyristate, cetearylisononanoate,isopropylmyristate, isopropylpalmitate, isopropylstearate,isopropyloleate, n-butylstearate, n-hexyllaureate, n-decyloleat,isooctylstearate, isononylstearate, isononylisononanoate, 2-ethylhexylpalmitate, 2-ethylhexyllaurate, 2-hexyldecylstearate,2-octyidodecylpalmitate, stearylheptanoate, oleyloleate, oleylerucate,erucyloleate, erucylerucate, tridecylstearate, tridecyltrimellitate, andsynthetic, half-synthetic or natural mixtures of such esters e.g. jojobaoil.

Other fatty components suitable for use in the formulation of thepresent invention include polar oils such as lecithines and fatty acidtriglycerides, namely triglycerinic esters of saturated and/orunsaturated, straight or branched carbonic acid with 8 to 24 carbonatoms, preferably of 12 to 18 carbon-atoms whereas the fatty acidtriglycerides are preferably chosen from synthetic, half synthetic ornatural oils (e.g. cocoglyceride, olive oil, sun flower oil, soybeanoil, peanut oil, rape seed oil, sweet almond oil, palm oil, coconut oil,castor oil, hydrogenated castor oil, wheat oil, grape seed oil,macadamia nut oil and others); apolar oils such as linear and/orbranched hydrocarbons and waxes e.g. mineral oils, vaseline(petrolatum); paraffins, squalan and squalen, polyolefines, hydrogenatedpolyisobutenes and isohexadecanes, favored polyolefines are polydecenes;dialkyl ethers such as dicaprylylether; linear or cyclic silicone oilssuch as preferably cyclomethicone(octamethylcyclotetrasiloxane),cetyldimethicone, hexamethylcyclotrisiloxane, polydimethylsiloxane,poly(methylphenylsiloxane) and mixtures thereof.

Still other fatty components which may advantageously be incorporatedinto formulations of the present invention include isoeikosane;neopentylglycol diheptanoate; propyleneglycol dicaprylate/dicaprate;caprylic/capric/diglycerylsuccinate; butyleneglycol caprylate/caprate;C₁₂₋₁₅-alkyllactates; di-C₁₂₋₁₅-alkyltartrates; triisostearin;dipentaerythrityl hexacaprylate/hexacaprate; propyleneglycolmonoisostearate; tricaprylin; dimethylisosorbid. Especially beneficialis the use of mixtures of C₁₂₋₁₅-alkylbenzoates and2-ethylhexylisostearate, mixtures of C₁₂₋₁₅-alkylbenzoates andisotridecylisononanoate as well as mixtures of C₁₂₋₁₅-alkylbenzoates,2-ethylhexylisostearate and isotridecylisononanoate.

The oily phase of the formulation of the present invention may alsocontain natural vegetable or animal waxes such as bee wax, china wax,bumblebee wax and other waxes of insects as well as shea butter andcocoa butter.

A moisturizing agent may be incorporated into a composition of thepresent invention to maintain hydration or rehydrate the skin.Moisturizers that prevent water from evaporating from the skin byproviding a protective coating are called emollients: Additionally anemollient provides a softening or soothing effect on the skin surfaceand is generally considered safe for topical use. Preferred emollientsinclude mineral oils, lanolin, petrolatum, capric, caprylictriglyceraldehydes, cholesterol, silicones such as dimethicone,cyclomethicone, almond oil, jojoba oil, avocado oil, castor oil, sesameoil sunflower oil, coconut oil and grape seed oil, cocoa butter, oliveoil aloe extracts, fatty acids such as oleic and stearic, fatty alcoholssuch as cetyl and hexadecylalcohol, diisopropyl adipate, hydroxybenzoateesters, benzoic acid esters of C₉₋₁₅-alcohols, isononyl iso-nonanoate,ethers such as polyoxypropylene butyl ethers and polyoxypropylene cetylethers, and C₁₂₋₁₅-alkyl benzoates, and mixtures thereof. The mostpreferred emollients are hydroxybenzoate esters, aloe vera, C₁₂₋₁₅-alkylbenzoates, and mixtures thereof. An emollient may be present in anamount of about 1 wt. % to about 20 wt. % of the total weight of thecomposition. The preferred amount of emollient may be about 2 wt. % toabout 15 wt. %, and most preferably about 4 wt. % to about 10 wt. %.

Moisturizers that bind water, thereby retaining it on the skin surfaceare called humectants. Suitable humectants may be incorporated into acomposition of the present invention such as glycerin, polypropyleneglycol, polyethylene glycol, lactic acid, pyrrolidon carboxylic acid,urea, phopholipids, collagen, elastin, ceramides, lecithin sorbitol,PEG-4, and mixtures thereof. Additional suitable moisturizers arepolymeric moisturizers of the family of water soluble and/orswellable/and/or with water gelating polysaccarides such as hyaluronicacid, chitosan and/or a fucose rich polysaccharide which is e.g.available as Fucogel®1000 (CAS-Nr. 178463-23-5) by SOLABIA S. One ormore humectants are optionally present at about 0.5 wt. % to about 8 wt.% in a composition of the present invention, preferably about 1 wt. % toabout 5 wt. %.

The aqueous phase of the compositions of the present invention maycontain usual cosmetic additives such as alcohols, especially loweralcohols, preferably ethanol and/or isopropanol, low diols oder polyolsand their ethers, preferably propylenglycols, glycerin, ethyleneglycol,ethyleneglycol monoethyl- or monobutyl-ether, propyleneglycol-monomethyl-, monoethyl- or monobutyl ether, diethyleneglycol-monomethyl-or monoethyl-ether and analogue products, polymers,foam stabilisators; electrolytes and especially one or more thickeners.Thickeners that may be used in formulations of the present invention toassist in making the consistency of a product suitable include carbomer,siliciumdioxide, magnesium and/or aluminum silicates, beewax, stearicacid, stearyl alcohol polysaccharides and their derivatives such asxanthan gum, hydroxypropyl cellulose, polyacrylamides, acrylatecrosspolymers preferably a carbopole, such as carbopole of type 980,981, 1382, 2984, 5984 alone or mixtures thereof. Suitable neutralizingagents which may be included in the composition of the present inventionto neutralize components such as e.g. an emulsifier or a foambuilder/stabilizer include but are not limited to alkali hydroxides suchas a sodium and potassium hydroxide; organic bases such asdiethanolamine (DEA), triethanolamine (TEA), aminomethyl propanol, andmixtures thereof; amino acids such as arginine and lysine and anycombination of any foregoing. The neutralizing agent may be present inan amount of about 0.01 wt. % to about 8 wt. % in the composition of thepresent invention, preferably, 1 wt. % to about 5 wt. %.

The addition of electrolytes into the composition of the presentinvention may be necessary to change the behavior of a hydrophobicemulsifier. Thus the emulsions/microemulsions of this invention maypreferably contain electrolytes of one or several salts including anionssuch as a chloride, a sulfate, a carbonate, a borate or an aluminate,without being limited thereto. Other suitable electrolytes may be on thebases of organic anions such as, but not limited to, lactate, acetate,benzoate, propionate, tartrate and citrate. As cations preferablyammonia, alkylammonia, alkali- or alkaline earth metals, magnesium-,iron- or zinc-ions are selected. Especially preferred salts arepotassium and sodium chloride, magnesium sulfate, zinc sulfate andmixtures thereof. Electrolytes are present in an amount of about 0.01wt. % to about 8 wt. % in the composition of the present invention.

The cosmetic compositions of the invention are useful as compositionsfor photoprotecting the human epidermis or hair against the damagingeffect of ultraviolet irradiation, as antisun/sunscreen composition oras makeup product. Such compositions can, in particular, be provided inthe form of a lotion, a thickened lotion, a gel, a cream, a milk, anointment, a powder or a solid tube stick and may optionally be packagedas an aerosol and may be provided in the form of a mousse, foam or aspray. When the cosmetic composition according to the invention isprovided for protecting the human epidermis against UV radiation or asantisun/sunscreen composition, it may be in the form of a suspension ordispersion in solvents or fatty substances, or alternatively in the formof an emulsion or microemulsion (in particular of O/W or W/O type, O/W/Oor W/O/W-type), such as a cream or a milk, a vesicular dispersion, inthe form of an ointment, a gel, a solid tube stick or an aerosol mousse.The emulsions can also contain anionic, nonionic, cationic or amphotericsurfactants.

When the cosmetic composition according to the invention is used forprotecting the hair, it may be in the form of a shampoo, a lotion, a gelor a rinse out composition, to be applied before or after shampooing,before or after dyeing or bleaching, before, during or afterpermanent-waving or hair straightening operation, a styling or treatmentlotion or a gel, a blow-drying or hairsetting lotion or gel, a hairlacquer, or a composition for permanent-waving, straightening, dyeing orbleaching the hair.

When the cosmetic composition according to the invention is used asmakeup product for eyelashes, the eyebrows, the skin or the hair, suchas an epidermal treatment cream, a foundation, a tube of lipstick, aneyeshadow, a face powder, an eyeliner, a mascara or a coloring gel, itmay be solid or pasty, anhydrous or in aqueous form, such as O/W or W/Oemulsion, suspension or gel.

The present invention also features formulating the organosiliconecompounds according to the invention as an agent for screening out UVradiation, in particular for controlling the color of human skin.

The organosilicone compounds according to this invention show anexcellent liposolubility and can thus be incorporated in highconcentrations into cosmetic formulations which leads to high protectionfactor of the final compositions. Additionally they are homogeneouslydistributed in the cosmetic formulation containing at least a fattyphase and an cosmetically accepted organic solvent which leads, appliedon the skin/or hair, to the formation of a protective film whichprotects effectively the skin and/or hair against the deleteriouseffects of UV-radiation.

Thus, it is another object of the present invention to use the compoundsof the invention for protecting the skin and/or hair against ultravioletradiation, in particular solar radiation, comprising topically applyingan effective amount of a cosmetic composition containing theorganosilicone compounds according to the invention.

Finally, this invention also features non-therapeutic regime/regimen forcontrolling the variation of the color of the skin caused by ultravioletradiation, comprising topically applying onto the skin an effectiveamount of a cosmetic composition containing organosilicone compoundsaccording to the invention.

According to another embodiment of the invention, a organosiliconecompound of this invention can be used as protecting agent against UVradiation for plastics.

The organosilicone derivatives of the invention are also photostable.

In accordance with the foregoing the invention provides

(1) An organosilicone compound for use as a UVA filter, e.g. for use ina cosmetic composition;

(2) A cosmetic composition comprising an organosilicone compound asunder (1) as active ingredient together with cosmetically acceptedadjuvants and additives, in particular a composition further comprisinga screening agent selected from the group consisting of UV-A screeningagents, UV-B screening agents, and mixtures thereof, e.g. acomplementary anorganic UV screening agent, such as a coated or uncoatedpigment or nanopigment of a metaloxide selected from the oxides oftitanium, zinc, iron, zirconium and cerium;

(3) A cosmetic composition comprising an organosilicone compound asunder (1) as active ingredient together with cosmetically acceptedadjuvants and additives for protecting human hair and/or skin againstdamage in which UVA irradiation plays a role or is implicated;

(4) A method to the protection of human hair and/or skin against damagein which UVA irradiation plays a role or is implicated which comprisestopically applying an effective amount of an organosilicone compound asunder (1);

(5) Use of an organosilicone compound as under (1) for protecting humanhair and/or skin against damage in which UVA irradiation plays a role oris implicated.

The following examples are provided to further illustrate the processesand compositions of the present invention. These examples areillustrative only and are not intended to limit the scope of theinvention in any way. In the Examples, FC. means Flash chromatography;HV means high vacuum (0.1 Pa or below); INCI means InternationalNomenclature Cosmetic Ingredients. All structures were unambiguouslyidentified via ¹H-NMR (300 MHZ, CDCl₃). The photostability of theproducts were measured according to Berset et. al.; Internat. J.Cosmetic Science 18:167-177 (1996).

EXAMPLE A1 Preparation of 2-(4-diethylamino-2-hydroxybenzoyl)benzoicacid prop-2-ynyl ester

A mixture of 32 mmol 2-(4-diethylamino-2-hydroxybenzoyl)benzoic acid,160 mmol propargylic alcohol and 32 mmol H₂SO₄ is refluxed for 48 h.After evaporation of the excess propargylic alcohol the residue isdissolved in ethylacetate and subsequently washed twice with saturatedNaHCO₃ solution and twice with water. After drying (Na₂SO₄), the solventis evaporated (HV) and the crude product purified twice via FC(n-hexane/EtOAC 1:1, hexane/MTBE 4/1-1/1) yielding2-(4-diethylamino-2-hydroxybenzoyl)benzoic acid prop-2-ynyl ester. MS(EI): 374 (18%, M+Na⁺), 352 (100%, M+H⁺), 296 (17%). UV (EtOH):λ_(max)=356 nm (ε=31′648).

EXAMPLE A2 Preparation of 2-(4-diethylamino-2-hydroxybenzoyl)benzoicacid allyl ester

A mixture of 32 mmol 2-(4-diethylamino-2-hydroxybenzoyl)benzoic acid,160 mmol allylic alcohol and 32 mmol H₂SO₄ is refluxed for 48 h. Afterevaporation of the excess allylic alcohol the residue is dissolved inethyl acetate and subsequently washed twice with saturated NaHCO₃solution and twice with water. After drying (Na₂SO₄), the solvent isevaporated (HV) and the crude product purified via FC (n-hexane/EtOAC2:1, hexane) yielding 2-(4-diethylamino-2-hydroxybenzoyl)benzoic acidallyl ester. MS (EI): 376 (10%, M+Na⁺), 354 (100%, M+H⁺), 296 (17%). UV(EtOH): λ_(max)=354 nm (ε=34′257).

EXAMPLE A3 Preparation of2-(4-diethylamino-2-hydroxybenzoyl)-propargylic benzamide

A mixture of 6 g of 2-(4-diethylamino-2-hydroxybenzoyl) benzoic acid and1.6 g of propargylic amine is dissolved in 20 ml of DMF with cooling toform a clear solution. 5.9 g of dicyclohexylcarbodiimide is slowly addedto this solution. The mixture is diluted with 20 ml of CH₂Cl₂ and leftat room temperature for two hours. The suspension formed is filtered andwashed with hexane and ether. The organic phase is diluted with EtOAc,washed with saturated NaHCO₃ solution, three times with water and oncewith saturated NaCl solution. After drying (Na₂SO₄), the solvent isevaporated (HV) and the crude product purified via FC (n-hexane/EtOAC2:1, hexane) and recrystallized from a mixture of hexane, toluene andEtOAc, yielding white crystals of2-(4-diethylamino-2-hydroxybenzoyl)-propargylic benzamide. MS: 351(M+H⁺), 333, 296 (100%).

EXAMPLE B1 Preparation of a COMPOUND wherein B, B′, R¹, R⁶, R⁷, R⁸, R⁹,R¹⁰ and R¹¹ are methyl, Z is a Group of Formula III wherein R³ and R⁴are ethyl and —X—Y— is —O—CH₂—C(CH₂)— (major isomer), r is in itsStatistical Mean 14 and s is in its Statistical Mean 4

A solution of 1.75 mmol of 2-(4-diethylamino-2-hydroxybenzoyl)benzoicacid prop-2-ynyl ester and 1.75 mmol eq. SiH of a COMPOUND wherein B,B′, R¹ and R² are methyl, Z is H, r is in its statistical mean 14 and sis in its statistical mean 4 (MW˜1500) in 3 ml toluene under an inertatmosphere is heated to 55° C. A catalytic amount of platinum carbon 5%is added and the reaction is kept at 55° C. for 20 h. The productsolution is washed with a mixture of water/methanol=1:10, dried(Na₂SO₄), and concentrated. After the residue is dissolved in 3 mltoluene, active charcoal is added and the mixture is stirred for 2 d atRT. After filtration over Celite the solvent is evaporated to yield ayellow oil (two isomers). UV (EtOH): 354 nm (E=477), having unlimitedsolubility in Cétiol LC and Crodamol DA and excellent photostabilityqualities in film.

EXAMPLE B2 Preparation of a COMPOUND wherein B, B′, R¹, R⁶, R⁷, R⁸, R⁹,R¹⁰ and R¹¹ are methyl, Z is a Group of Formula III wherein R³ and R⁴are ethyl and —X—Y— is —O—CH₂—C(CH₂)— (Major Isomer), r is in itsStatistical Mean 60 and s is in its Statistical Mean 4

0.5 g of 2-(4-diethylamino-2-hydroxybenzoyl)benzoic acid prop-2-ynylester, 2 g of polysiloxane AE-151 of Wacker-Chemie GmbH, and a catalyticamount of platinum carbon 5% in 10 ml of xylene are placed in athree-necked reaction flask under an inert atmosphere and heated for 2 hat 70° C. The product solution is filtered through Celite, washed with amixture of water/methanol=1:10 and concentrated to yield a brownish oil(two isomers). UV 354 nm (E=147), having unlimited solubility in CétiolLC and Crodamol DA and excellent photostability qualities in film.

EXAMPLE B3 Preparation of a COMPOUND wherein B, B′, R¹, R⁶, R⁷, R⁸, R⁹,R¹⁰ and R¹¹ are methyl, Z is a Group of Formula III wherein R³ and R⁴are ethyl and —X—Y— is —NH—CH₂—C(CH₂)— (Major Isomer), r is 0 and s is 1

A solution of 1.4 mmol of2-(4-diethylamino-2-hydroxybenzoyl)-propargylic benzamide and 1.2 mmolof heptamethyltrisiloxane of formula IV wherein B, B′, R¹ and R² aremethyl, Z is hydrogen, r is 0 and s is 1, in 10 ml of toluene under aninert atmosphere is heated to 55° C. A catalytic amount ofplatinum-divinyl-tetramethyl-disiloxane complex is added and thereaction is kept at 80 to 85° C. for 36 hours and at 100° C. for fourhours. 0.3 g of additional heptamethyltrisiloxane and a small amount ofcatalyst are added. After heating for another 18 hours at reflux, theproduct solution is concentrated and chromatographed twice (CH₂Cl₂/MeOH)to yield the product (two isomers). UV (EtOH): 358 nm (E=227).

EXAMPLE C1 Preparation of a Broad Spectrum Sunscreen Lotion Containing2% of a Organosilicone Compound of the Invention

Part wt % compound INCI name A 2.00 PARSOL MCX octyl methoxycinnamate2.00 organosilicone compound of the invention 3.00 PARSOL 1789 4-tert.butyl-4′-methoxy- dibenzoyl-methane 12.00 CETIOL LCcoco-caprylate/caprate 4.00 DERMOL185 isostearyl neopentanoate 0.25diethyleneglycolmonostearate PEG-2-stearate 1.00 cetylalcoholcetylalcohol 0.25 MPOB/PPOB methyl-propylparabene 0.10 EDTA BDEDTA-disodium salt 1.00 AMPHISOL DEA diethanolamine cetylphosphate B20.00 PERMULENE TR-1 (+%) Acrylate C10-C30 Alkylacrylate 48.60 deionizedwater deionized water 5.00 propyleneglycol 1,2-propanediol 0.80 KOH(10%) potassium hydroxide

Part A is heated in a reactor to 85° C. Part B is slowly added within 10minutes, followed by addition of KOH, cooling and degassing of theemulsion.

EXAMPLE C2 Preparation of a Broad Spectrum Sunscreen Lotion Containing4% of a Organosilicone Compound of the Invention

Part wt % compound INCI name A 3.00 PARSOL MCX octyl methoxycinnamate4.00 organosilicone compound of the invention 3.00 PARSOL 5004-methylbenzylidene camphor 4.00 PARSOL 1789 4-tert. butyl-4′-methoxy-dibenzoyl-methane 2.00 glyceryl monostearate glyceryl stearate 2.00cetylalcohol extra cetylalcohol 2.00 GANEX V-220 PVP/eicosene copolymer4.00 CERAPHYL 375 isostearyl neopentanoate 4.00 CERAPHYL 847octyldodecyl stearoyl stearate 2.00 AMPHISOL K potassium cetylphosphate0.10 EDTA BD EDTA-disodium salt 0.60 PHENONIP phenoxyethanol & methyl,ethyl, propyl & butyl paraben B 11.15 deionized water deionized water50.00 CARBOPOL 934 (1% solution) carbomer 5.00 propyleneglycol1,2-propanediol 0.15 NIPAGIN M methylparaben 3.00 KOH (10%) potassiumhydroxide q.s. perfume oil fragrance

Part A is heated in a reactor to 85° C. The homogeneous Part B is addedfollowed by addition of preheated KOH (75° C.), cooling and degassing ofthe emulsion.

EXAMPLE C3 Preparation of a Broad Spectrum Sunscreen Cream Containing 4%of a Polysiloxane Compound of the Invention

Part wt % compound INCI name A 8.00 PARSOL SLX dimethico-diethylbenzalmalonate 4.00 organosilicone compound of the invention 6.00T-COTE 031 titanium dioxide & dimethicone 10.00 ESTOL GTEH 3609trioctanoin 1.00 cetyl alcohol cetyl alcohol 4.00 ESTOL GMM 3650glyceryl myristate 0.05 butylated hydroxytoluene BHT 0.10 EDTA BDdisodium EDTA 0.60 PHENONIP phenoxyethanol & methyl-, ethyl-propyl- &butyl-paraben 2.00 AMPHISOL K potassium cetyl phosphate B 50.75deionized water deionized water 10.00 CARBOPOL 980 1% solution Carbomer980 3.00 glycerin glycerin C 0.50 KOH 10% solution potassium hydroxideq.s perfume oil fragrance

Part A is heated to 85° C. while stirring and then mixed for 30 secondswith a turbine at 8000 t/minutes. When homogeneous, Part B is pre-heatedto 75° C. and added to Part A. The mixture is cooled to 40° C. and PartC is added. The water loss is compensated and stirring is continuedwhile cooling to ambient temperature. Then the mixture is mixed for 30seconds with a turbine at 8000 t/minute.

The cream has a low skin penetration quality.

1. An organosilicone compound comprising a unit of formula I

wherein a is 0, 1 or 2, R¹ is hydrogen, a saturated or unsaturatedC₁-C₃₀hydrocarbon group or a trimethylsilyloxy group; and Z is an aminosubstituted hydroxybenzophenone of formula III

wherein R³ and R⁴ independently are hydrogen, C₁-C₂₀alkyl,C₂-C₂₀alkenyl, C₃-C₁₀cycloalkyl or C₃-C₁₀cycloalkenyl or R³ and R⁴,together with the nitrogen atom they are bound to, form a 5 to 6membered ring; X is —O— or —NR⁵— wherein R⁵ is hydrogen, C₁-C₂₀alkyl,C₂-C₂₀alkenyl, C₃-C₁₀cycloalkyl or C₃-C₁₀cycloalkenyl; and Y is adivalent C₃-C₁₂alkylene or alkenylene chain; and, optionally, a unit offormula II

wherein b is 0, 1, 2, 3; and R² is hydrogen, a saturated or unsaturatedC₁-C₃₀hydrocarbon group or a trimethylsilyloxy group.
 2. A lineardiorgano-siloxane polymer comprising one structural unit of formula IVaand one structural unit of formula IVb

s units of formula IVc

and r units of formula IVd

wherein Z is as defined in claim 1; R¹, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹independently are as defined in claim 1 for R²; B and B′ independentlyare a group Z or a group R²; r is an integer from 0 to 200; and s is aninteger from 0 to 50, wherein at least B or B′ is Z when s is
 0. 3. Aprocess for the preparation of an organosilicone compound according toclaim 1 comprising reacting (hydrosilylating) an organosilicone compoundcomprising a unit of formula VI

wherein a is 0, 1 or 2; and R¹ is hydrogen, a saturated or unsaturatedC₁-C₃₀hydrocarbon group or a trimethylsilyloxy group; and, optionally, aunit of formula II according to claim 1, with a compound of formula VII

in which R³, R⁴ and X are as defined in claim 1 and Y′ has the samedefinition as Y in claim 1, but is terminated either with a double or atriple bond.
 4. A cosmetic composition comprising an organosiliconecompound as in claim 1 together with cosmetically accepted adjuvants andadditives.
 5. A cosmetic composition comprising an organosiliconecompound as in claim 1 for protecting human hair and/or skin againstdamage in which UVA irradiation plays a role or is implicated.
 6. Amethod to the protection of human hair and/or skin against damage inwhich UVA irradiation plays a role or is implicated which comprisestopically applying an effective amount of an organosilicone compound asin claim
 1. 7. Use of an organosilicone compound as in claim 1 forprotecting human hair and/or skin against damage in which UVAirradiation plays a role or is implicated.
 8. (canceled)